Photographic color process utilizing 2-pyrazolin-5-one couplers

ABSTRACT

PHOTOGRAPHIC COLOR MATERIAL COMPRISING IN A LIGHTSENSITIVE SILVER HALIDE EMULSION LAYER OR IN A NON-LIGHTSENSITIVE WATER-PERMEABLE COLLOID LAYER IN WATER-PERMEABLE RELATIONSHIP COLLOID LAYER IN WATER-PERMEABLE RELATIONSHIP WITH THE SAID EMULSION LAYER A MAGENTAFORMING COLOR COUPLER OF THE 2-PYRAZOLIN-5-ONE TYPE WHEREIN SAID COLOR COUPLER CONTAINS IN THE 1-POSITION A PHENYL GROUP CARRYING AT LEAST ONE HALOALKYLOXY GROUP, HALOALKYLTHIO GROUP OR HALOALKYLSULPHONYL GROUP. THE PHOTOGRAPHIC COLOR MATERIALS AS A RESULT OF THE SELECT COLOR COUPLER HAVE NARROW SPECTRAL ABSORPTION CURVES AND, THEREFORE, SHOW LITTLE SIDE ABSORPTION IN THE UNDESIRABLE REGIONS OF THE SPECTRUM AND, ADDITIONALLY, HAVE GOOD MOISTURE AND LIGHT STABILITY.

United States Patent Office 3,623,871 Patented Nov. 30, 1971 US. Cl. 96-56.5 8 Claims ABSTRACT OF THE DISCLOSURE Photographic color material comprising in a lightsensitive silver halide emulsion layer or in a non-lightsensitive water-permeable colloid layer in water-permeable relationship with the said emulsion layer a magentaforming color coupler of the 2-pyrazolin-5-one type wherein said color coupler contains in the 1-position a phenyl group carrying at least one haloalkyloxy group, haloalkylthio group or haloalkylsulphonyl group. The photographic color materials as a result of the select color coupler have narrow spectral absorption curves and, therefore, show little side absorption in the undesirable regions of the spectrum and, additionally, have good moisture and light stability.

This invention relates to 2-pyrazolin-5-one colour couplers, to the preparation thereof, to photographic elements containing such colour couplers as well as to colour development processes wherein said colour couplers take part in the formation of a magenta dye image.

It is known that for the manufacture of a photographic colour image in a light-sensitive silver halide emulsion layer the exposed silver halide is developed to a silver image by means of an aromatic primary amino compound in the presence of a colour coupler, which by reaction with the oxidized developer forms a dye on the areas corresponding with the silver image.

In the subtractive three-colour photography usually a light-sensitive photographic colour material is used comprising a red-sensitized, a green-sensitized and a bluesensitive silver halide emulsion layer wherein on development by means of suitable colour couplers, a cyan, a magenta and a yellow dye image are formed respectively.

In many of the known I-aryI-Z-pyrazolin-S-one colour couplers for magenta the aryl group in the 1-position has been a benzene ring containing substituents such as halogen atoms, alkyl groups, alkyloxy groups, alkylthio groups, alkylsulphonyl groups.

These 1-aryl-2-pyrazolin-5-one colour couplers comprise in the 3-position a group mainly serving as ballasting group, which renders the colour coupler less liable to diffuse from a photographic colloid layer in which it is incorporated. However, if it is desired to make colour couplers which are ditfusible this can be done by appropriate choice of the substituent in the 3-position i.e. by a substituent of low molecular weight. These substituents in the 3-position of l-aryl-2-pyrazolin-5-one colour couplers for magenta include alkylamino, arylamino, acylamino, acyloxyamino, and ureido groups examples of which can be found in literature, see for example United Kingdom patent specifications 909,318 and 1,069,534, United States patent specifications 2,369,489, 3,325,482, 3,330,660 and 3,393,071, Japanese patent publication 7039/57 and German patent specification 1,176,479.

According to the present invention novel 2-pyrazolin- 5-one colour couplers for magenta are provided having in the l-position a phenyl group carrying at least one haloalkyloxy group, haloalkylthio group or haloalkylsulphonyl group, preferably a Cl HCSO group, a ClH CSO group, a ROF20- group, a RCF S- group and a RCF SO group, wherein R stands for hydrogen, fluorine or polyhaloalkyl such as --CI-IF -CHFCl, 'SHFBr, -CFCl CCl -CHFCF etc.

The colour couplers according to the present invention can be represented by the following general Formula I:

1 1 O=C/ \N Hg -NH-Rx wherein:

Q stands for haloalkyloxy, haloalkylthio or haloalkylsulphonyl for instance Cl HCSO ClH C-4O' RCF O, RCF S and RCF SO wherein R has the same significance as above,

Z stands for hydrogen, halogen such as chlorine, alkyl, alkoxy, alkylthio, alkylsulphonyl or for the group Q having the same significance as above, and

R stands for an alkyl group, an aryl group, an acyl group, such as alkylcarbonyl, alkylsulphonyl, aralkylcarbonyl, aralkylsulphonyl, arylcarbonyl and arylsulphonyl, a carbamoyl group such as alkylcarbamoyl, aralkylcarbamoyl and arylcarbamoyl, or an acyloxy group such as alkoxycarbonyl, aryloxycarbonyl and aralkyloxycarbonyl; the group R may carry substituents favourable influencing the physical, spectral and/ or scnsitometric properties of the colour couplers and the dyes formed therewith such as halogen, sulpho, carboxy, alkoxy and phenoxy which may in turn be substituted e.g. by halogen, sulpho, carboxy and alkyl.

The colour couplers of the present invention are distinguished from the known 2-pyrazolin-5-one colour couplers by having attached to the nitrogen atom in the l-position of the 2-pyrazolin-5-one nucleus a benzene ring carrying at least one haloalkyloxy group, haloalkylthio group or haloalkylsulphonyl group. The colour couplers of the present invention have useful properties not shared by the known couplers of similar structure; one such useful property is that the magenta dyes produced on development have favourable spectral and sensitometric properties e.g. they have less broad spectral absorption curves and thus show little side-absorptions in the undesirable regions of the spectrum and another that they have an improved moistand light-stability as compared with dyes similarly produced from the said known l-aryl- 2-pyrazolin-5-one colour couplers.

For manufacturing an appropriate photographic multilayer colour material containing colour couplers for each colour separation image in the differently optically sensitized silver halide emulsion layers, the colour couplers must be present in the hydrophilic silver halide emulsion layers or other colloid layers in water-permeable relationship therewith in a non-ditfusible form.

For the purpose of rendering the colour couplers according to the present invention less liable to diffusion from photographic colloid layers in which they are incorporated the colour couplers of the present invention can be provided in the 3-position of the 2-pyrazolin-5- one nuclei with a ballasting group. For instance, the group R can be or contain a substituent of the formula -X-D wherein D is an acyclic aliphatic hydrocarbon residue with from 5 to 20 carbon atoms and X stands for a chemical bond, oxygen, sulphur, sulphonyl,

Another interesting method of rendering the colour couplers fast to diffusion in photographic colloid layers is to use the colour couplers in polymeric form e.g. by copolymerisation of monomeric colour couplers according to the present invention carrying in the 3-position an ethylenic group such as the group wherein Y stands for hydrogen, halogen, lower alky'l, aralkyl or aryl, with one or more non-colour forming monomers containing at least one ethylenic group.

The present invention therefore further provides monomeric 2-pyrazolin-5-one colour couplers corresponding to the above general formula wherein R stands for an acyl group of the formula wherein Y has one of the significances given above as well as polymeric colour couplers comprising recurring units of the following general Formula II:

wherein Z, Q and Y have the same significance as above.

The following are representative colour couplers of the present invention. However it is to be understood that the invention is not limited to these specific couplers.

3. SP -CHF;

so H :0 N a l n l mro o-Q-o (c11 MUM-3 H 0 C-NHC O- (CH2) 14- 3 Sim-CHI SIOZCFQ The non-diffusing colour couplers according to the present invention carrying a ballasting group in the 3- position can be incorporated into the photographic material according to any technique known by those skilled in the art for incorporating photographic ingredients, more particularly colour couplers, into colloid compositions. For instance the water-soluble colour couplers e.g. those containing one or more sulpho or carboxyl groups (in acid or salt form) can be incorporated into the coating composition of the layer in question from an aqueous solution if necessary in the presence of alkali and the water-insoluble or insufficiently water-soluble colour couplers from a solution in the appropriate Water-miscible or waterimmiscible high-boiling or low-boiling organic solvents or mixtures thereof whereupon the solution obtained is dispersed, if necessary in the presence of a wetting or dispersing agent, in a hydrophilic colloid composition forming or forming part of the binding agent of the colloid layer. The hydrophilic colloid composition may of course comprise in addition to the colloid carrier all other sorts of ingredients.

The polymeric colour couplers can be incorporated into photographic colloid compositions according to any technique known by those skilled in the art for incorporating polymeric photographic colour couplers into colloid compositions. For instance they can be dissolved in water, in water-miscible or water-immiscible solvents or mixtures of solvents whereupon the solution obtained is dissolved or dispersed, if necessary in the presence of a Wetting or dispersing agent, in a hydrophilic colloid composition forming or forming part of the binding agent of the colloid layer. The polymeric colour couplers can also be incorporated into hydrophilic colloid compositions in the form of latices, primary latices as well as secondary latices.

The solutions of the colour couplers of the above general formula or of the polymeric colour couplers as well as the colour coupler latices need not necessarily be dispersed or dissolved directly in the coating composition of the silver halide emulsion layer or other waterpermeable layer. Said solution may advantageously be first dispersed or dissolved in an aqueous non-light-sensitive hydrophilic colloid solution whereupon the resultant mixture, if necessary, after the removal of the organic solvents employed, is intimately mixed with the said coating composition of the light-sensitive silver halide emulsion layer or other water-permeable layer just before coating.

For more details about particularly suitable dispersing techniques that can be employed for incorporating the non-ditfusing colour couplers of the invention carrying a ballasting group into a hydrophilic colloid layer of a photographic material there can be referred to United Kingdom patent specifications 791,219, 1,098,594, 1,099,- 414, 1,099,415, 1,099,416 and 1,099,417, to French patent specification 1,555,663, to United States patent specification 2,304,940, and to Belgian patent specification 722,026.

For details as to the preparation of polymeric colour couplers and latices therefrom as well as to the incorporation of said polymeric colour couplers into photographic colloids there can be referred to Belgian patent specification 669,971, to United Kingdom patent specification 1,130,581 and to co-pending United Kingdom patent application 9,218/68.

The colour couplers according to the present invention may be used in conjunction with various kinds of photographic emulsions. Various silver salts may be used as the sensitive salt, such as silver bromide, silver iodide, silver chloride, or mixed silver halides, such as silver chlorobromide, silver bromoiodide and silver chlorobromoiodide. The couplers can be used in emulsions of the mixed-packet type, such as described in United States patent specification 2,698,794 or emulsions of the mixedgrain type as described in United States patent specification 2,592,243. The colour couplers can be used with emulsions wherein latent images are formed predominantly on the surface of the silver halide crystal, or with emulsions wherein latent images are formed predominantly inside the silver halide crystal.

The hydrophilic colloid used as the vehicle for the silver halide may be, for example, gelatin, colloidal albumin, zein, casein, a cellulose derivative, a synthetic hydrophilic colloid such as polyvinyl alcohol, poly-N-vinylpyrrolidone, etc. If desired, compatible mixtures of two or more of these colloids may be employed for dispersing the silver halide.

The light-sensitive silver halide emulsions of use in the preparation of a photographic material according to the present invention may be chemically as well as optically sensitized. They may be chemically sensitized by efiecting the ripening in the presence of small amounts of sulphur containing compounds such as allyl thiocyanate, allyl thiourea, sodium thiosulphate, etc. The emulsions may also be sensitized by means of reductors for instance tin compounds as described in French patent specification 1,146,955 and in Belgian patent specification 568,687, imino-amino methane sulphinic acid compounds as described in United Kingdom patent specification 789,823 and small amounts of noble metal compounds such as of gold, platinum, palladium, iridium, ruthenium and rhodium. They may be optically sensitized by means of cyanine and merocyanine dyes.

The said emulsions may also comprise compounds which sensitize the emulsions by development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in U.S. patent specifications 2,531,832, 2,533,790, 3,210,191 and 3,158,484, in United Kingdom patent specifications 920,637 and 991,608 and in Belgian patent specification 648,710 and onium derivatives of amino-N-oxides as described in United Kingdom patent specification 1,121,- 696. Further the emulsions may be stabilized with heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-Z-thione and 1-phenyl-2-tetrazoline-5-thione and compounds of the hydroxy-triazdo-pyrimidine type. They can also be stabilized with mercury compounds such as the mercury compounds described in Belgian patent specifications 524,121, 677,337, and 707,386 in and in U.S. patent specification 3,179,520.

The light-sensitive emulsions may also comprise all other kinds of ingredients such as plasticizers, hardening agents, wetting agent, etc.

The colour couplers for magenta described in the present invention are usually incorporated into a green-sensitized silver halide emulsion for forming one of the diiferently sensitized silver halide emulsion layers of a photographic multilayer colour material. Such photographic multilayer colour material usually comprises a support, a red-sensitized silver halide emulsion layer with a colour coupler forcyan, a green-sensitized silver halide emulsion layer with a colour coupler for magenta and a blue-sensitive silver halide emulsion layer with a colour coupler for yellow.

The emulsions can be coated on a wide variety of photographic emulsion supports. Typical supports include cellulose ester film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film, and related films of resinous materials, as well as paper and glass.

For the production of photographic colour images according to the present invention an exposed silver halide emulsion layer is developed preferably with an aromatic primary amine developing substance in the presence of a colour coupler according to the present invention.

Suitable developing agents are atomatic compounds, such as p-phenylene diamine, N,N'-dialkyl-p-phenylene diamines such as N,N-diethyl-p-phenylenediamine, and derivatives such as N,N-dialkyl-N'-sulphomethyl-p-phenylenediamines and N,N-dialkyl-N-carboxymethyl-p-phenylene diamines.

The 1-aryl-2-pyrazolin-5-one colour couplers according to the above general Formula I wherein R stands for an aryl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an aralkyloxycarbonyl group can be prepared, e.g. by application of one of the methods described in United Kingdom patent specifications 909,318 and 1,069,534, in United States patent specifications 2,369,489, 3,325,482, 3,330,- 660 and 3,393,071, in Japanese patent publication 7039/57 and in German patent specification 1,176,479, starting from the corresponding 1-aryl-3-amino-2-pyrazolin-5-one compound.

The monomeric 1-aryl-2-pyrazolin-5-one colour couplers carrying in the 3-position an acylamino group of the formula wherein Y is hydrogen, halogen, lower alkyl, aralkyl or aryl, can be prepared from the corresponding l-aryl-3- amino-2-pyrazolin-5-one compounds according to one the methods described in co-pending application 9,218/ 68.

The 1-aryl-3-amino-2-pyrazolin-5-one compounds used in said methods can be prepared according to the method known by those skilled in the art by cyclisation of an appropriately substituted phenyl hydrazine with e.g. the ethyl ester of ,B-imino-B-ethoxy-propionic acid.

Hereinafter are given some preparations to illustrate how the 1-aryl-3-amino-2-pyrazolin-5-one compounds of use for the preparation of the colour couplers of the invention can be prepared. For the preparation of the colour couplers of the invention some specific syntheses of representative colour couplers are given.

(A) PREPARATION OF 1-ARYL-3-AMINO-2-PYRA- ZOLIN-S-ONE COMPOUNDS Preparation l.1-p-trifluoromethylsulphonylphenyl- 3-amino-2-pyrazolin-5-one 22 g. of p-trifluoromethylsulphonylphenyl hydrazine prepared as described in Bull. Soc. Chim. Belg. 74, 270 (1965) and 18 g. of ethyl B-ethoxy-fl-imino-propionate hydrochloride in 50 ml. of pyridine are heated for 1 hour at 40 C. on a water-bath. The reaction mass becomes solid and acetonitrile is added. The white precipitate is filtered by suction.

To 22 g. of the precipitate formed 20 ml. of tetramethyl guanidine is added whereupon the mixture is kept for 30 min. on a boiling water bath. The mixture is then diluted with water and the solution formed is acidified by addition of 2 N hydrochloric acid. The precipitate is filtered by suction and recrystallized from toluene to which a little acetonitrile was added. Melting point: 188 C.

Preparation 2.1-p-difiuoromethylsulphonylphenl-3- amino-Z-pyrazolin-S-one 222 g. of p-difiuoromethylsulphonylphenyl hydrazine prepared as described in Bull. Soc. Chim. Belg. 74, 270 (1965), 200 g. of ethyl B-ethoxy-fi-imino-propionate hydrochloride and 4 ml. of acetic acid are melted on a waterbath of 90 C. The homogeneous melt obtained is stirred for 1 hour at 40 C. while evaporating under reduced pressure by means of a Water jet pump the ethanol formed.

A solution of 46 g. of sodium in 700 ml. of methanol is added and the mixture is heated for 30 min. at 50 C. After dilution with water the solution is acidified and the precipitate formed is filtered by suction. The precipitate is washed with Water and recrystallized from ethylene glycol monomethyl ether. Melting point: 219 C.

Preparation 3.1-p-(1,1,2-trifluoro-2-chloroethoxy)- phenyl-3-amino-2-pyrazolin-5-one (a) 113 g. of p-(l,1,2-trifiuoro-2-chloroethoxy)aniline are added to 200 ml. of concentrated hydrochloric acid (d 1.19) and 75 ml. of water. A white precipitate forms. The mixture is cooled to 5 C. whereupon the componnd is diazotised by addition at 5 C. of 35 g. of sodium nitrite in 175 ml. of water. Then the mixture is stirred for 30 min.

The cold diazonium solution is added to a solution of 337.5 g. of tin(II) chloride-Z-water in 350 ml. of concentrated hydrochloric acid (1111.19) at C. The mixture is stirred for 2 hours at 10 C. whereupon it is gradually heated on a water-bath to 60 C. The mixture is filtered while warm and the precipitate is washed with a saturated solution of sodium chloride heated to 60 C. The precipitate is suspended in 10 N sodium hydroxide and extracted with benzene. The benzene solution is dried over magnesium sulphate and distilled under reduced pressure. Boiling point: 120 C./1 mm.

(b) 72 g. of p-(1,1,2-trifluoro-2-chloroethoxy)phenyl hydrazine prepared in step (a), 60 g. of ethyl ,B-ethoxy- B-imino-propionate and 1.8 ml. of acetic acid are left standing for 30 min. at room temperature. The mixture is stirred for 1 hour at 50 C., while evaporating under reduced pressure by means of a water jet pump the ethanol formed.

A solution of 14 g. of sodium in 250 ml. of ethanol is added whereupon the mixture is kept for 1 hour at room temperature. The mixture is diluted with water and then acidified by means of acetic acid. The precipitate formed is recrystallized from methanol. Melting point: 158 C.

Preparation 4.1-o-(l,1,2-trifluoro-2-chloroethoxy)- phenyl-3-arnino-2-pyrazolin-5-one (a) 900 g. of o-(1,1,Z-trifiuoro-2-chloroethoxy)aniline (Bull. Soc. Chim. France 1957, 581) are stirred in 2.4 litres of 5 N hydrochloric acid and diazotised at 5 C. by means of 280 g. of sodium nitrite dissolved in 600 ml. of water. The solution is filtered whereupon it is added to a solution of 2080 g. of tin(II) chloride-2-water in 2080 ml. of concentrated hydrochloric acid. The mixture is stirred for 1 hour and the precipitate is filtered by suction. The precipitate is washed with a 20% aqueous solution of sodium chloride.

The precipitate is suspended in a mixture of 4 litres of water and 4 litres of benzene whereupon 2 litres of 10 N sodium hydroxide are added. The mixture is heated with stirring to 60 C. The benzene layer is separated and the aqueous layer is extracted with benzene. The benzene solutions are dried over magnesium sulphate, concentrated by evaporation and distilled under reduced pressure. Boiling point: 125 C./1 mm.

(b) 48 g. of o-(1,1,2-trifiuoro-2-chloroethoxy)-phenyl hydrazine prepared in step (a), 40 g. of ethyl fi-ethoxy- B-imino-propionate and 1.2 ml. of acetic acid are stirred for 90 min. Then a solution of 9.2 g. of sodium in methanol is added and the temperature rises to 30 C. The mixture is cooled to room temperature and stirred for 2 hours. The ethanol is evaporated, the mixture is diluted with water and then acidified. The precipitate is filtered by suction an drecrystallised from acetonitrile. Melting point: 168 C.

Preparation 5.-1-o-difiuoromethylthiophenyl-3-amino- 2-pyrazolin-5-one (a) In a 2 litre reaction vessel provided with stirrer, 800 ml. of diethylene glycol dimethyl ether and 320 g.- of potassium hydroxide are placed with stirring. After the addition of ml. of water the potassium hydroxide dissolves completely. In the solution obtained 125 g. of oamino-thiophenol are dissolved whereupon the solution is heated to 40 C. and diifuorochloromethane is introduced for 2 hours. The temperature rises to 60-65 C. When a precipitate forms water is added. The organic layer is separated and the aqueous layer is extracted with ether. The ether is removed by evaporation under reduced pressure and the residue is acidified by means of alcoholic 6 N hydrochloric acid. The crystalline precipitate formed is filtered off, washed with ether and the crude product is recrystallised from acetic acid. Melting point: 180 C. (sublimation).

(b) In a 1 litre three-necked flask fitted with stirrer, thermometer and dropping funnel 120 ml. of 5 N hydro chloric acid and ml. of water are placed. With stirring 63 g. of o-difluoromethylthio aniline hydrochloride from step (a) are added. The product is diazotised at 51 C. by adding dropwise a solution of 22.8 g. of sodium nitrite in 60 ml. of water. The mixture is stirred till all precipitate is dissolved. The solution is filtered and cooled to 0 C. Then a solution of 187.5 g. of sodium sulphite in 225 m1. of water is added as quickly as possible.

The reaction mixture is heated to 70 C. and the precipitate formed dissolves. Then the solution is acidified by means of 25 ml. of hydrochloric acid (d:1.19) and the reaction mixture is kept for 4 hours at 6570 C. During the night the mixture is allowed to cool to room temperature. The precipitate formed is filtered off and redissolved in water. The solution is neutralised by addition of 2 N sodium hydroxide whereupon it is extracted 3 times with ether. The ether extracts are collected and concentrated by evaporation until all ether has evaporated. The remainnig oil is distilled under reduced pressure. Boiling point: 120 C./l.5 mm.

(c) A mixture is made of 50 g. of o-difiuoromethylthiophenyl hydrazine, 60 g. of ,B-ethoxy-fl-imino-propionic acid ether ester and 1.5 ml. of acetic acid. The mixture is kept for 30 min. at room temperature whereupon a solution of 12 g. of sodium in 150 ml. of methanol is added. The solution is heated for 30 min. at 40 C. whereupon the solvent is removed by evaporation underreduced pressure. The residue is taken up in water and neutralized with diluted acetic acid. The 3-amino-2-pyrazolin-S-one separates as the monohydrate. It is recrystallised from methanol. Melting point: 60 C.

Preparation 6.1p-( 1,1 ,2-trifiuoro-2-chloroethylsulphonyl) -phenyl-3-amino-2-pyrazolin-5-one (a) 117 g. of p (1,1,2 trifiuoro-Z-chloroethylsulphonyl)-chlorobenzene in ml. of ethanol are refluxed for 16 hours in the presence of 64 g. of anhydrous hydrazine. The reaction mixture is concentrated by evaporation and treated with water. The precipitate formed is 11 filtered by suction and recrystallized from ethanol. Melting point: 102 C.

(b) 29 g. of p (1,1,2 trifiuoro 2-chloroethylsulphonyl)-phenyl-hydrazine, 20 g. of B-ethoxy-fi-iminopropionic acid ethyl ester and 0.5 ml. of acetic acid are stirred for 1 hour and then left standing at room temperature for 24 hours. The w-amidrazone crystallizes and after filtration is washed with n-hexane. Then a solution of 4.6 g. of sodium in 70 ml. of methanol is added and after 30 min. the solution formed is diluted with 125 ml. of water and poured into 200 ml. of 1 N sulphuric acid. The precipitate formed is filtered oil and recrystallized from ethanol. Melting point: 168 C.

Preparation 7.--1-(2-chloro-S-chloromethylsulphonylphenyl) 3amino-Z-pyrazolin-S-one (a) 4-chloro-3-nitrophenyl chloromethyl sulphone are added with stirring to a solution of 1140 g. of tin(II) chloride in 1800 ml. of concentrated hydrochloric acid, which has been heated to 70 C., in such away that the temperature rises rapidly to 100 C. The temperature is kept at 100 C. by the further addition of the above sulfone. When 410 g. of the above sulfone has been added the mixture is stirred for 30 min. at 95100 C.

The mixture is cooled and the liquid decanted whereupon the precipitate is washed twice with 2 litres of 20% hydrochloric acid. The precipitate is filtered by suction and the moist filter cake is treated with water till all hydrochloride is converted into the free amine. Melting point: 89-93 C.

(b) 140 g. of the 2-chloro5-chloromethylsulphonylaniline obtained in step (a) are dissolved in 570 ml. of acetic acid by heating on a water-bath. The solution is filtered and admixed with 1750 ml. of concentrated hydrochloric acid. The mixture is stirred for 10 min. and then diazotised at 20 to 5" C. by means of 42 g. of sodium nitrite in 100 ml. of water. The mixture is stirred for 1 hour at 5 C., and then filtered whereupon it is poured at 20 C. into a solution of 280 g. of tin(II) chloride in 300 ml. of water. After the addition of 700 ml. of water the mixture is stirred again for 2 hours at 20 C.

The mixture is left standing overnight at 20 C., filtered by suction and the residue dissolved in water. The aqueous solution is neutralized with ammonium hydroxide and the precipitate formed after having been filtered by suction and dried, is recrystallized from 600 ml. of ethanol. Melting point: 100-105 C.

(c) 60 g. of fl-ethoxy-B-imino-propionic acid ethyl ester and 63.5 g. of 2-chloro-5-chloromethylsulphonylphenyl hydrazine are dissolved by gently heating in 250 ml. of ethanol. By addition of acetic acid the pH of the solution is adjusted to about 6 whereupon the solution is left standing for 4 hours at room-temperature. 100 ml. of a 30% solution of sodium methylate in methanol are added and the solution is left standing overnight and then acidified with acetic acid. The mixture is left standing for 2 hours at 0 C. whereupon the precipitate formed is filtered by suction and washed with cold methanol. Melting point: 193-195 C.

Preparation 8.--lm-dichloromethylsulphonylphenyl-3- amino-2-pyrazolin-5-one (a) 112 g. of dichloromethyl phenyl sulphone prepared as described by Brugnatelli, I. Prakt. Chem. 2, 40, 541, are dissolved in 140 ml. of sulphuric acid monohydrate whereupon at 20 C. 50 ml. of nitric acid (1111.52) are added dropwise. The temperature is kept at 20-25 C. by cooling with ice-water. The mixture is then stirred for 2 hours at room temperature and poured in 3 litres of ice-water. The precipitate formed is filtered by suction and washed with water till neutral. Melting point: 90-100" C.

(b) 128 g. of m-nitrophenyl dichloromethyl sulphone are portion-wise added with stirring at 80 C. to a solution of 410 g. of tin(II) chloride in 612 ml. of concentrated hydrochloric acid. The temperature rises to 105 C. The

12 mixture is stirred for 45 min. at -l00 C. and then cooled at 20 C. The precipitate formed is filtered by suction and the filter cake treated with water. From the clear solution the free amine precipiates. Melting point: 155 C.

(c) 51.5 g. of m-dichloromethylsulphonylaniline in 322 ml. of 2 N hydrochloric acid and ml. of water are diazotised at 0-5 C. with a solution of 15 g. of sodium nitrate in 43 ml. of water. The mixture is stirred for 30 min. and filtered. The filtrate is added at once to a sulphite solution prepared by introducing sulphur dioxide in a solution of 43 g. of sodium hydroxide in 345 ml. of water. The solution is heated in 15 min. to 80 C. and stirred for 40 min. at this temperature. The pH is kept at 7.3-7.5 and then the mixture is acidified by means of ml. of concentrated hydrochloric acid and heated for 3 hours at 8090 C. The warm solution is filtered, admixed with 100 ml. of concentrated hydrochloric acid and concentrated by evaporation under reduced pressure whereby the hydrazine hydrochloride precipitates.

(d) 43.5 g. of m-dichloromethylsulphonylphenyl hydrazine hydrochloride in 135 ml. of methanol are neutralized by means of a 30% solution of sodium methylate in methanol and then admixed with 33 g. of j3-ethoxy-fl-imino-propionic acid ethyl ester. After the addition of 4 ml. of acetic acid the mixture is refluxed for 45 min. 48 ml. of a 30% solution in methanol of sodium methylate are added whereupon the mixture is refluxed again for 30 min. Then, the mixture is poured into 1 litre of water, filtered and acidified with acetic acid. The precipitate formed is filtered by suction and washed with water. Melting point: 260270 C.

(B) PREPARATION OF THE COLOUR COUPLERS Preparation 9.-Compound 4 In a three-necked flask equipped with stirrer, thermometer and reflux condenser fitted with a drying tube, 26.7 g. of anhydrous aluminium chloride and 28 g. of l-p-difluoromethylsulphonylphenyl 3-amino-2-pyrazolin-5-one are dissolved in 70 ml. of nitrobenzene. Then, 27.5 g. of palmitoyl chloride are added dropwise while keeping the mixture at 4045 C. Hydrogen chloride is evolved. The mixture is stirred for 1 hour and then poured in 100 ml. of concentrated hydrochloric acid (d :1.19) and 500 ml. of ice. The precipitate formed is filtered off, taken up in acetonitrile, cooled to room temperature and recrystallized from ethylene glycol monomethyl ether. Melting point: 178 C.

Preparation 10.Compound 6 In a three-necked flask fitted with stirrer, thermometer and reflux condenser 20 g. of anhydrous aluminium chloride, and 15.35 g. of lptrifluoromethylsulphonylphenyl- 3amino-2-pyrazolin-5-one are dissolved in 100 ml. of nitrobenzene. Then, 15 g. of octadecylisocyanate are added dropwise. The temperature rises to 50 C. and the mixture is stirred for 3 hours.

The precipitate formed upon pouring the reaction mixture into 200 ml. of 2 N hydrochloric acid is washed with water and melted under water. The nitrobenzene is separated. The white precipitate formed by pouring into methanol is filtered by suction and recrystallized from ethanol. Melting point: 210 C.

Preparation 11.Compound 9 22 g. of l-odifluoromethylthiophenyl-3amino-Z-pyrazolin-S-one hydrate are dehydrated by addition of benzene and the azeotropic mixture of water and benzene is removed. The reaction mixture is placed in a 250 ml. flask fitted with reflux condenser whereupon 21.2 g. of palmitoyl chloride are added and the mixture is refluxed for 2 hours. Acetonitrile is added and refluxing is continued for 2 hours. The mixture is concentrated by evaporation till half its volume and made alkaline by means of 13 2 N sodium hydroxide. After having been heated for 30 min. at 40 C. the mixture is acidified by means of acetic acid. The oil obtained solidifies by scratching with a glass rod. The product is recrystallized from acetonitrile. Melting point: 78 C.

Preparation 12.-Compound In a 250 ml. three-necked flask fitted with stirrer and reflux condenser 13.4 g. of aluminium chloride are dissolved in 100 ml. of pyridine. To this solution 15.4 g. of 1-o-(1,1,3-trifluoro-2-chloroethoxy) phenyl 3 amino-2- pyrazolin-S-one are added. The mixture is stirred for 20 min. whereupon 19 g. of p-hexadecyloxybenzoylchloride are added in room temperature. After having been stirred for min. the reaction mixture is kept for 3 hours at 40-46" C. The mixture is concentrated till dry by evaporation and the solid product is dissolved in warm ethylene glycol monomethyl ether. 250 ml. of hydrochloric acid (d :1.19) are added and the oil obtained is separated whereupon ice is added. The precipitate formed is filtered by suction and washed first with warm Water and then with cold water.

The crude product is dissolved in warm methanol and the solution is made alkaline by addition of 1 N sodium hydroxide, diluted with water and acidified by means of acetic acid. The oil formed solidifies upon standing and the precipitate is filtered off, washed twice with warm water and dried. The colour coupler is recrystallized from methanol. Melting point: 88 C.

Preparation 13.Compound 11 In a 500 ml. flask fitted with reflux condenser are placed 28.9 g. (0.1 mole) of 1-p-difluoromethylsulphonylphenyl- 3-amino-2-pyrazolin-5-one, 41.7 g. of Z-hexadecyloxy-S- carboxy-aniline hydrochloride and 200 ml. of acetic acid. The mixture is refluxed for 2 hours and then poured into Water. The precipitate formed is filtered off, washed with Water, boiled in acetonitrile and filtered again while warm. After having been dried the residue is recrystallized from ethylene glycol monomethyl ether. Melting point: 193 C.

Preparation 14.Compound 12 In a three-necked flask fitted with stirrer, thermometer and reflux condenser 13.4 g. of anhydrous aluminium chloride are dissolved in 100 ml. of pyridine. Then 15.4 g. of 1-o-(1,1,2-trifluoro-2-chloroethoxy)phenyl-3-amino- 2-pyrazolin-5-one are added and the mixture is stirred for min. At room temperature, 16.5 g. of arachidoyl chloride are added and the reaction mixture is then heated for 3 hours at 40-45 C. The mixture is concentrated till dry by evaporation under reduced pressure and the residue is dissolved in ethylene glycol monomethyl ether and 250 ml. of hydrochloric acid d 1.19) The oil formed solidifies by addition of ice. The solids are filtered off and washed first with water of 60 C. and then with cold water.

The crude product is purified by dissolving in methanol, making alkaline by means of 1 N sodium hydroxide, dilution with water and acidifying with acetic acid. The oil formed solidifies upon standing. The precipitate is washed twice with water and dried. The product is recrystallized from methanol. Melting point: 72 C.

Preparation 15.Compound 13 To a solution of 15.4 g. of 1-p-(1,1,2-trifluoro-2-chloroethoxy)phenyl-3-amino-2-pyrazolin-5-one in 12 ml. of pyridine and 88 ml. of acetonitrile, 24.25 g. of hexadecylsulphonylchloride are added. The mixture is stirred for 16 hours and the precipitate formed is filtered off and dissolved in alkaline ethanol. The preciiptate is filtered off and the filtrate neutralised by addition of acetic acid. The precipitate that forms is dried and after repeated recrystallisation from ethanol the melting point is 166 C.

Preparation 16.Compound 14 A solution of 30.75 g. of 1-p-(1,1,2-trifluoro-2-chloroethoxy)phenyl-3-amino-2-pyrazolin-5-one and 10.5 g. of

14 methacryloyl chloride in 50 ml. of acetonitrile is refluxed for 4 hours. The solution is diluted with water and the precipitate formed is filtered off and purified by recrystallisation from acetonitrile. Melting point: 190 C.

Preparation 17.-Copolymer of methyl acrylate and l-p- (1,1,2 trifluoro-2-chloroethoxy)phenyl-3-methacryloyl-amino-2-pyrazolin-5-one In a 500 ml. flask fitted with stirrer, thermometer, reflux condenser, dropping funnel and inlet tube for nitrogen are placed 185 ml. of demineralised water, 2.4 g. of the sodium salt of oleyl methyl tauride, 15.65 g. of l-p- (1,1,2 trifiuoro 2-chloroethoxy)phenyl-3-methacryloylamino-2-pyrazolin-5-one and 32.3 g. of methyl acrylate. The suspension is stirred for 20 min. and then under nitrogen atmosphere heated to the reflux temperature. Then, 2.4 ml. of a 5.8% aqueous solution of 4,4-azo-bis(4-cyanovaleric acid) are added and polymerisation is allowed to proceed for 2 hours at -90 C. The latex formed is cooled and a little residue is filtered off. Yield: 180 ml. of latex.

Concentration of solids per 10 ml. of latex: 20.3 g.

Equivalent molecular weight (i.e. the number of grams of polymer containing 1 mole of polymerized monomeric colour coupler): 1418.

Preparation 18.--Compound 15 (a) 2-tetradecyl-4-chloro-5-methylphenol.1000 g. of 4-chloro-m-cresol are melted at 70 C. in an oil bath whereupon 14 g. of boron trifluoride are added in 10 min. Then 393 g. of l-tetradecene are added dropwise at 70 C. in 2 hours. The mixture is stirred for 1 hour and then poured into a mixture of 2 litres of water and 0.9 litre of 30% aqueous sodium hydroxide. Two layers form of which the underlying layer is removed. The oily upper layer is washed twice with aqueous sodium hydroxide and then treated with diluted hydrochloride acid. The layer is taken up in 600 ml. of methylene chloride and dried. The methylene chloride is removed by evaporation and the residue distilled under reduced pressure. Boiling point: 165170 C./0.5 mm. Yield: 520 g.

(b) 2 (2-tetradecyl-4-chloro-5-methylphenoxy)-etha nol.In a solution of 34.5 g. of sodium in 260 ml. of methanol, 408 g. of 2-tetradecyl-4-chloro-5-methylphenol are dissolved with stirring whereupon 73.5 g. of 2-chloroethanol are added. After 3 hours another 73.5 g. of 2- chloroethanol are added and the mixture is then left standing overnight.

The mixture is boiled for 3 hours with stirring and then added to 2 litres of water and thoroughly stirred. The water is removed and the oily layer dissolved in 600 ml. of methylene chloride. By addition of acetic acid and washing with water the methylene chloride solution is made neutral. After the removal of the methylene chloride 420 g. of a high viscous oil remains which is used as such in the next reaction step.

(c) 2 (2-tetradecyl-4-chloro-5-methylphenoxy)ethyl chloroformate.--l50 g. of phosgene are introduced for 40 minutes with stirring into 950 ml. of dry toluene. Then a mixture of 400 g. of the above viscous oil, 126 g. of dimethylaniline and ml. of toluene is added dropwise in about 3 hours. The mixture is left standing overnight whereupon 600 ml. of cold water are added and the excess of phosgen is removed completely by means of an air current introduced into the reaction mixture. The water is separated from the toluene solution whereupon the latter is diluted with hydrochloric acid and washed with water. After the removal of the toluene by distillation about 440 g. of dry residue remains which consists of about 92- 95% of the above chloroformate.

((1) Compound 15.37 g. of anhydrous aluminium chloride are admixed with 180 ml. of ethylene chloride whereupon 550 ml. of pyridin are added at once. To the clear solution obtained are added at 40 C. g. of l-p- (1,1,2 trifluoro-2-chloroethylsulphonyl)-phenyl-3-amino- 2-pyrazolin-5-one whereupon 175 g. of the above chloroformate are added at once with stirring at a temperature of 40 C. The mixture is stirred for 40 min. at 50-60 C. whereupon it is poured into a mixture of 0.8 litre of concentrated hydrochloric acid, 1 litre of methanol and 1 liter of ethyl acetate. After having stirred the mixture for 10 min. the mixture is mixed with 3 litres of water and the ethyl acetate solution is separated. The later is solution is diluted with hydrochloric acid and washed with water till neutral. The ethyl acetate is removed by evaporation under reduced pressure and the residue is dissolved in petroleum naphtha. The solution is left standing overnight and 125 g. of component separate therein. Melting point: 107-1 12 C.

Preparation 19.Compound 16 To a suspension of 22 g. of anhydrous aluminium chloride in 70 ml. of ethylene chloride, 320 ml. of dry pyridin are added at once with stirring and cooling by means of ice-water. To the hot solution 66 g. of l-(2- chloro--chloromethylsulphonyl) 3 amino-2-pyrazolin- 5-one are added. The mixture is stirred at about 40 C. whereupon 100 g. of 1-(2-tetradecyl-4-chlorophenoxy) ethyl chloroformate, prepared in an analogous way as the ethyl chloroformate in preparation 19, are added. The mixture is stirred for 1 hour at 50-60 C. and then poured into a mixture of 400 ml. of concentrated hydrochloric acid, 500 ml. of methanol and 500 ml. of ethyl acetate. The mixture is then further treated as described in preparation 18. Melting point: 80-83 C.

Preparation 20.-Compound 17 To a suspension of 11 g. of anhydrous aluminum chloride in 50 ml. of ethylene chloride, 160 ml. of dry pyridin are added at once with stirring and cooling by means of ice-water. To the clear pyridin solution 32 g. of l-m-dichloromethylsulphonylphenyl 3 amino-2-pyrazolin-5- one are added portion-wise at 20 C. When everything has dissolved 46 g. of 2-(2-tetradecyl-4-chlorophenoxy) ethyl chloroformate are added at once at 35 C. The temperature rises to 50 C. and the mixture is kept at said temperature for 40 min. whereupon it is poured into a mixture of 200 ml. of concentrated hydrochloric acid, 250 ml. of methanol and 250 ml. of ethyl acetate.

The mixture is stirred for minutes and then admixed with 800 ml. of water. The ethyl acetate layer that has been separated is washed till neutral with diluted hydrochloric acid and water. The ethyl acetate is removed by evaporation under reduced pressure and the residue dissolved in petroleum naphtha. 33 g. of compound 17 separates in the solution. Melting point: 50-59 C.

The following examples illustrate the use of the magenta-forming colour couplers according to the present invention.

Example 1.--117 g. of silver bromoiodide emulsion (2.3 mole percent of iodide), which comprises per kg. an amount of silver halide equivalent to 47 g. of silver nitrate and 73.4 g. of gelatin, are diluted with 192.5 g. of a 7.5% aqueous solution of gelatin and 200 g. of distilled water. To the emulsion obtained is added a gelatin gel comprising a dispersion of colour coupler No. 12 prepared by admixing by means of an ultrasonic wave generator a solution of 0.006 mole of said colour coupler in 14 ml. of ethyl acetate with 100 ml. of a 5% solution of gelatin and removing the ethyl acetate by evaporation under reduced pressure. After neutralization of the emulsion and addition of the common additives such as stabilizers, wetting agents and hardeners the necessary amount of distilled water is added to obtain 720 g.

The emulsion obtained is coated on a cellulose triacetate support pro rata of 125 g. per sq.m. The emulsion layer is dried and overcoated with a gelatin antistress layer.

After drying, the material formed is exposed for sec. through a continuous wedge with constant 0.30 and 1 6 then developed for 8 min. at 20 C. in a developing bath of the following composition:

Water to make 1 litre.

The developed material is treated for 2 min. at 18-20 C. in an intermediate bath comprising g. of sodium sulphate in 1 litre of water.

The material is rinsed for 15 min. with water and treated ina bleach bath of the following composition:

Borax 20 Anhydrous potassium bromide 15 Anhydrous sodium bisulphite 4.2 Potassium hexacyanoferrateflll) 100 Water to make 1 litre.

After bleaching, the material is rinsed with water for 5 min. and fixed in an aqueous solution of 200 g. of sodium thiosulphate per litre.

After a final rinsing for 15 min. the material is dried.

A magenta coloured wedge image is obtained having an absorption maximum of 534 nm.

Examples 2 and 3.Example 1 is repeated with the difference that colour coupler 12 is replaced by 0.006 mole of colour couplers 2 and 10.

Magenta coloured wedge images are obtained both having absorption maxima of 5 34 nm.

Example 4.-ll7 g. of a silver bromoiodide emulsion (2.3 mole percent of iodide), which comprises per kg. an amount of silver halide equivalent to 47 g. of silver nitrate and 73.4 g. of gelatin, are diluted with 192.5 g. of a 7.5 aqueous solution of gelatin and 200 g. of distilled water. To the emulsion obtained is added a solution of colour coupler 8, prepared by dissolving at 55 C. 0.006 mole of the colour coupler in 44 ml. of ethanol, 6 ml. of 2 N sodium hydroxide and 32 ml. of distilled water. After neutralization and addition of the common emulsion additives such as stabilizers, Wetting agents, and hardeners the necessary amount of distilled water to obtain 720 g. of emulsion is added whereupon the emulsion is coated on a cellulose triacetate support pro rata of g. per sq.m. The emulsion layer is dried and overcoated with a gelatin antistress layer.

Exposure and processing occurs as described in Example 1.

A magenta coloured wedge image having an absorption maximum of 5 38 nm. is obtained.

Examples 59.Example 4 is repeated with the dilference that colour coupler 8 is replaced by 0.006 mole of colour couplers l, 3, 4, 5 and 7 respectively.

Magenta coloured wedge images are obtained having absorption maxima at 538 nm., 544 nm., 538 nm., 542 nm. and 540 nm. respectively.

Example 10.-10 g. of colour coupler 15 are dissolved in 30 ml. of ethyl acetate whereupon the solution is dispersed by means of a high speed mixer in ml. of a 5% aqueous solution of gelatin. The ethyl acetate is removed by evaporation whereupon the gelatin gel comprising a dispersion of colour coupler 15 is admixed with a conventional green-sensitized silver halide emulsion.

The emulsion obtained is coated on a cellulose triacetate supoprt whereuon it is dried and overcoated with a gelatin antistress layer.

After exposure and processing as described in Example 1 a transparent magenta coloured image is obtained showing a high colour density with little side absorption in the blue and red region of the spectrum.

The dye image has a high dye intensity with 3 1 tion maximum of 545 nm.

Examples 1112.Example is repeated with the difference that colour coupler 15 is replaced by colour couplers 16 and 17 respectively.

Magenta coloured dye images are obtained having absorption maxima at 544 and 534 nm. respectively.

We claim:

1. Process for the production of a photographic colour image by development of a photographic element comprising image-wise exposed silver halide with the aid of an aromatic primary amino developing agent wherein said development is carried out in the presence of a magentaforming colour coupler of the Z-pyrazolin-S-one type containing in the l-positon a phenyl group carrying at least one haloalkyloxy, haloalkylthio or haloalkylsulphonyl group, thus forming a magenta azomethine dye by reaction of the said colour coupler with the developing agent being converted in its oxidized form by reduction of the exposed silver halide.

2. Process according to claim 1 wherein said colour coupler of the Z-pyrazolin-S-one type corresponds to the following formula:

H doNHR1 wherein: Q stands for haloalkyloxy, haloalkylthio or haloalkylsulphonyl,

Z stands for hydrogen, halogen, alkyl, alkoxy, alkylthio,

alkylsulfphouyl, or the group Q, and R stands for an alkyl group, an aryl group, an acyl group,

a carbamoyl group or an acryloxy group.

3. Photographic colour material comprising in a lightsensitive silver halide emulsion layer or in a non-lightsensitive water-permeable colloid layer in water-permeable relationhip with the said emulsion layer a magentaforming colour coupler of the Z-pyrazolin-S-one type wherein said colour coupler contains in the 1-position a phenyl group carrying at least one haloalkyloxy group, haloalkylthio group or haloalkylsulphonyl group.

4. Photographic colour material according to claim 3 wherein said colour coupler corresponds to the formula:

haloalkyl- Z stands for hydrogen, halogen, alkyl, alkoxy, alkylthio,

alkylsulphonyl, or the group Q, and R stands for an alkyl group, an aryl group, an acyl group,

a carbamoyl group or an acyloxy group.

5. Photographic colour material according to claim 4 wherein the substituent R comprises a group rendering the colour coupler fast to diffusion in photographic colloid layers and corresponding to the formula X-D wherein D is an acyclic aliphatic hydrocarbon residue with from 5 to 20 carbon atoms and X stands for a chemical bond, oxygen, sulphur, sulphonyl, CONH, NHCO, SO N(R with R =hydrogen or alkyl, NHSO or N(alkyl).

6. Photographic colour material according to claim 3, wherein said colour coupler is a polymer having recurring units of the formula:

wherein: Z stands for hydrogen, halogen, alkyl, alkoxy, alkylthio,

alkylsulphonyl, or the group Q,

Q stands for haloalkyloxy, haloalkylthio or haloalkylsulphonyl, and

Y stands for hydrogen, halogen, lower alkyl, aralkyl or aryl.

7. Photographic colour material according to claim 3, wherein the said haloalkyloxy, haloalkylthio or haloalkylsulphonyl group is the group RCF O, RCF S- or RCF SO wherein R stands for hydrogen, fluorine or polyhaloalkyl.

8. Photographic colour material according to claim 3, wherein the said haloalkylsulphonyl group is Cl HCSO or ClH CSO References Cited UNITED STATES PATENTS 8/1969 Eynde et al 96-100 7/1970 Moubaliu et al. 9656.5

J. TRAVIS BROWN, Primary Examiner 

